Naphthostyril dyestuffs

ABSTRACT

The subject of the invention are dyestuffs of the formula ##STR1## wherein R is hydrogen or a hydrocarbon radical 
     Q is aryl 
     X is ═C(W) -- or ═N--, 
     W is a nitrile ester or amide groups and 
     A represents the remaining members of a heterocyclic radical. 
     The dyestuffs are preferably suitable for dyeing polyester fibres which are dyed in orange, red, violet or bluish shades with good fastness to light.

The invention relates to dyestuffs of the general formula ##STR2##wherein R represents hydrogen, alkyl, alkenyl, aralkyl, cycloalkyl, arylor a 2-membered or 3-membered alkylene radical which is linked to theadjacent o-position of the ring a,

Q represents aryl or an o-arylene radical linked to the adjacentperi-position of the ring b,

X represents ═C(W)-- or ═M--,

W represents CN, CONW¹ W², COOW³ or a radical of the formula ##STR3##W¹, W² and W³ each represent hydrogen or alkyl and W¹ and W², conjointlywith the common N atom, can also form a saturated 5-membered or6-membered heterocyclic ring and

A represents the remaining members of a 5-membered or 6-membered,quasi-aromatic, optionally benzo-condensed heterocyclic radical, and thecyclic and acyclic radicals can contain the substituents customary indyestuff chemistry,

and processes for their preparation, their use for dyeing high-molecularweight organic materials and materials dyed with these dyestuffs.

Within the scope of the invention, "substituents customary in dyestuffchemistry" are understood as, in particular, non-ionic radicals, that isto say radicals which do not confer solubility in water, as well ascationic and anionic radicals. Suitable cationic radicals are ammonium,cycloammonium and guanidinium radicals. Suitable anionic radicals aresulpho, sulphinatio, sulphato, disulphimide and carboxylate groups.Suitable non-ionic radicals are those defined in more detail below.

Alkyl radicals R preferably have 1-8 C atoms and can be interrupted by1-2 oxygen atoms. Particularly preferred radicals are C₁ -C₆ -alkylradicals and, in particular, C₁ -C₃ -alkyl radicals can bemonosubstituted by OH, Cl, Br, CN, C₁ -C₄ -alkoxycarbonyl, carboxyl,carbamoyl, C₁ -C₄ -alkylcarbonyl or phenoxy. Examples which may bementioned are: methyl, ethyl, β-cyanoethyl, β-chloroethyl,β-hydroxyethyl, β-hydroxy-n-propyl, β-hydroxy-γ-chloro-n-propyl,β-carboxyethyl, β-carbomethoxyethyl, β-carbethoxyethyl,β-carbobutoxyethyl, β-phenoxyethyl, β-carbamoylethyl, β-acetoxyethyl,β-methoxyethyl, β-ethoxyethyl, β-N-butoxyethyl, n-propyl, n-butyl,isobutyl, isoamyl and n-hexyl.

An alkenyl radical R which may be mentioned is the allyl radical.

Suitable aralkyl radicals R are, for example, phenyl-C₁ -C₃ -alkylradicals, which can be substituted in the phenyl nucleus, for example bychlorine, bromine, C₁ -C₄ -alkyl or C₁ -C₂ -alkoxy. Preferred cycloalkylradicals R are cyclohexyl radicals which can also carry 1-3 methylgroups.

Aryl radicals R which may be mentioned are phenyl radicals, which can besubstituted, for example by chlorine, bromine, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy.

Preferred alkylene radicals R which are linked to the adjacento-position of the ring a correspond to the formula --CH₂ --CH₂ -- or--CH₂ --CH₂ --CH₂ --.

Suitable aryl radicals Q are, above all, phenyl radicals, which can bemonosubstituted to disubstituted by C₁ -C₄ -alkyl, monosubstituted by C₁-C₂ -alkoxy, monosubstituted to pentasubstituted by chlorine,monosubstituted to pentasubstituted by bromine or monosubstituted byamino, acylamino, such as C₁ -C₄ -alkylcarbonylamino, C₁ -C₄-alkylsulphonylamino, phenylcarbonylamino, phenylsuphonylamino, acyloxy,such as C₁ -C₄ -alkylcarbonyloxy, phenylcarbonyloxy orphenylsulphonyloxy radicals, which can carry, as substituents, forexample C₁ -C₄ -alkyl, C₁ -C₂ -alkoxy or chlorine, and alkylsuphonyloxyradicals which have at least 4 C atoms in the alkyl radical, hydroxyl,nitro or --SO₂ --T, wherein T represents Cl, O-T¹ or NT² T³ and T¹denotes hydrogen, an optionally substituted alkyl radical with at least4 C atoms, preferably a C₄ -C₆ -alkyl radical, an optionally substitutedcycloalkyl radical, preferably a cyclohexyl radical which is optionallysubstituted by 1-3 methyl groups, a phenyl-C₁ -C₃ -alkyl radical or anoptionally substituted aryl radical, preferably a phenyl radical whichis optionally substituted by CH₃, Cl or CH₃ O, T² represents a C₁ -C₄-alkyl radical which is optionally substituted by OH, Cl, CN, C₁ -C₄-alkoxy, di-(C₁ -C₂ -alkyl)-amino or tri-C₁ -C₂ -alkylammonium, or aphenyl-C₁ -C₂ -alkyl radical, cyclohexyl, cyclohexylmethyl or a phenylradical which is optionally substituted by Cl, CH₃, OCH₃ or OC₂ H₅ andT³ represents hydrogen, a C₁ -C₄ -alkyl radical which is optionallysubstituted by OH, Cl, CN or C₁ -C₄ -alkoxy, or phenyl-C₁ -C₂ -alkyl or,conjointly with T², represents the remaining members of a 5-membered,6-membered or 7-membered heterocyclic ring, such as pyrrolidine,piperidine, perhydroazepine, morpholine, piperazine or N'-C₁ -C₄-alkylpiperazine (including the N'-β-hydroxyethyl derivative) or of aN',N'-di-(C₁ -C₄ -alkyl)piperazinium radical. A further suitable arylradical Q is the naphthyl radical.

o-Arylene radicals Q, which are linked to the adjacent peri-position ofthe ring b, are preferably o-phenylene radicals, which can besubstituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine, bromine or SO₂-T.

Heterocyclic radicals ##STR4## preferably belong to the3,3-dimethylindolenine, imidazole, benzimidazole, pyrazole, indazole,oxazole, benzoxazole, thiazole, benzthiazole, 1,3,4-thiadiazole,1,2,4-triazole, pyridine, quinoline, pyrimidine or quinazoline seriesand these radicals can carry substituents, preferably non-ionicsubstituents, such as C₁ -C₄ -alkyl, C₁ -C₂ -alkoxy, amino, nitro,chlorine, bromine, cyano or phenyl.

When X denotes ═C(W)--, ##STR5## preferably represents a radical of theformula ##STR6## wherein Z represents O, S, NR¹, C(CH₃)₂ or --NH--CO--and

R¹ represents hydrogen or alkyl.

Preferred substituents in the ring d are, for example, 1-2 C₁ -C₄-alkyls, including trifluoromethyl, 1 C₁ -C₄ -alkoxy, 1-2 chlorines or 1bromine, cyano, cyclohexyl, phenyl, phenyl-C₁ -C₃ -alkyl, C₁ -C₄-alkylsulphonyl, phenylsulphonyl or SO₂ T, in which T has theabovementioned meaning.

As further substituents, the ring a can contain, for example, chlorine,bromine, C₁ -C₂ -alkyl or a radical of the type Q-S- and the ring b cancontain, for example, C₁ -C₂ -alkoxy, chlorine, bromine or a radical ofthe type Q-S-.

Preferred alkyl radicals W¹, W² and W³ contain 1-4 C atoms and, inparticular, W³ can also contain 1 substituent, such as C₁ -C₄ -alkoxy orchlorine. Particularly preferred alkyl radicals W¹, W² and W³ aremethyl, ethyl, n-propyl and n-butyl. W preferably represents CN, COOC₁-C₂ -alkyl or COOH and in particular represents CN.

Preferred dyestuffs of the formula I correspond to the formula ##STR7##wherein E represents hydrogen, methyl, ethyl, β-cyanoethyl,β-chloroethyl, β-acetoxyethyl, β-methoxyethyl, β-ethoxyethyl,β-hydroxyethyl, β-carbomethoxyethyl, β-carboethoxyethyl, n-propyl,isopropyl, n-butyl, n-pentyl, benzyl, β-phenylethyl or phenyl orconjointly with E¹ represents --CH₂ --CH₂ --CH₂ --,

M represents a phenyl radical which is optionally monosubstituted topentasubstituted by chlorine, monosubstituted to disubstituted bybromine, monosubstituted to disubstituted by C₁ -C₄ -alkyl ormonosubstituted by phenyl, methoxy, ethoxy, phenoxy, a carboxylic acidC₁ -C₂ -alkyl ester, amino or acetylamino, or a naphthyl group orconjointly with E² represents a o-phenylene radical which is optionallysubstituted by methyl, chlorine, bromine, methoxy or ethoxy,

E¹ represents hydrogen, ethyl, chlorine, bromine or phenylmercapto orits methyl or chlorine derivative, E² represents hydrogen, chlorine,bromine, methoxy, ethoxy or phenylmercapto or its methyl or chlorinederivative,

X¹ represents ═C(W')-- or ═N--,

W' represents CN, COOH, COO-C₁ -C₂ -alkyl or a ##STR8## radical and Brepresents the remaining members of a radical of the thiazole-(2)-,1,2,4-thiadiazole-(3)-, 1,3,4-thiadiazole-(2)-, 1,2,4-triazole-(3)-,pyrimidine-(2)-, quinoline-(2)-,3,3-dimethylindolenine-(2)-pyridine-(2)-, benzthiazole-(2)-,benzoxazole-(2)- or benzimidazole-(2)-series, which can contain, assubstituents, 1-2 C₁ -C₄ -alkyls, 1-2 chlorines or 1 bromine, C₁ -C₂-alkoxy, C₁ -C₂ -alkylsulphonyl, di(C₁ -C₂ -alkyl)-aminosulphonyl,phenyl, cyclohexyl, nitro or amino.

When X=═C(W')--, B preferably represents the remaining members of aradical of the formula ##STR9## ps wherein Z¹ represents O, S, NH orC(CH₃)₂,

S¹ represents hydrogen or methyl or, conjointly with

S², represents --CH═CH--CH═CH--,

S² represents hydrogen, C₁ -C₄ -alkyl, cyclohexyl, phenyl, chlorine,bromine, C₁ -C₂ -alkoxy, C₁ -C₂ -alkoxy, carbonyl, C₁ -C₂-alkylsulphonyl or di-C₁ -C₂ -alkyl-amino,

S³ represents hydrogen, C₁ -C₂ -alkoxy, methyl, chlorine or di-C₁ --C₂-alkylamino-sulphonyl and

S⁴ represents hydrogen or chlorine.

When X=═N--, B preferably represents the remaining members of athiazole-(2)-, 1,2,4-thiadiazole-(3)-, 1,3,4-thiadiazole-(2)-,1,2,4-triazole-(3)-, pyrimidine-(2)-, quinoline-(2)- radical, andespecially of a pyridine-(2)- or benzthiazole-(2)- radical, whichradicals are optionally substituted by methyl, chlorine, bromine, C₁ -C₂-alkoxy, nitro, amino or phenyl.

Preferred substituents for the two last-mentioned ring systems aremethoxy, ethoxy, methyl, chlorine and amino.

Compounds which are particularly valuable industrially correspond to theformula ##STR10## wherein V represents hydrogen, methyl, ethyl,β-cyanoethyl, β-chloroethyl, n-propyl, n-butyl, benzyl or β-phenylethyl,

U represents a phenyl radical which is optionally monosubstituted topentasubstituted by chlorine, monosubstituted to disubstituted bybromine, monosubstituted to disubstituted by methyl or monosubstitutedby p-tertiary-butyl, methoxy or amino, or a naphthyl group or,conjointly with U², represents a o-phenylene radical which is optionallysubstituted by methyl, chlorine, bromine, methoxy or ethyoxy,

U¹ and U² each represent hydrogen, chlorine, bromine, phenylmercapto,tolylmercapto or chlorophenylmercapto,

X² represents ═C(CN)--, ═C(COO-C₁ -C₂ -alkyl)-- or ═N-- and D representsthe remaining members of a pyridyl-(2)- or 6-aminopyridyl-(2)-radical orof an azole radical of the formula ##STR11## wherein Z¹ represents O, Sor NH

U³ represents hydrogen, methyl, p-tertiary-butyl, methoxy, chlorine,phenyl or ethylsulphonyl,

U⁴ represents hydrogen, methyl, methoxy, ethoxy or chlorine and

U⁵ represents hydrogen or chlorine.

When X=═N--, Z¹ preferably represents S and V, U³ and U⁵ preferablyrepresent hydrogen.

When X² =═C(CN)-- or ═C(COO-C₁ -C₂ -alkyl)--, D preferably representsthe remaining members of an azole radical of the formula IV.

Particularly preferred radicals V are methyl and ethyl, as well ashydrogen.

The new compounds of the formula I can be prepared according to methodswhich are in themselves known. One of the processes is to subjectcompounds of the formula ##STR12## wherein R, Q, a and b have theabovementioned meaning and

Y represents ═O, ═Cl₂ or ═S or its S-C₁ -C₃ -alkyl derivative, to acondensation reaction with compounds of the formula ##STR13## wherein Xand A have the abovementioned meaning.

The condensation reaction is carried out under conditions which are inthemselves known, such as are indicated, for example, in GermanOffenlegungsschriften (German Published Pat.) Nos. 2,357,442, 1,931,789and 1,569,692/3, German Patent No. 1,247,513 and French Pat. No.1,388,599. When Y=O, the condensation reaction is carried out in thepresence of POCl₃ in an inert organic solvent, such as chlorobenzene,dichlorobenzene or perchloroethylene, in the temperature range of60°-140° C., and preferably at 80°-115° C. The components V and VI areemployed in an approximately molar ratio and, in general, an excess ofVI (for example 2-15%) is not troublesome.

The molar ratio of POCl₃ to the components V and VI can be about0.65-1.1 to 1, but a larger excess is also not troublesome.

The dyestuffs are frequently obtained primarily in the form of theiracid salts, which are converted into the neutral form by subsequenttreatment with customary acid-binding agents, such as K₂ CO₃, NaHCO₃ orpyridine, or in some cases are also already converted into the neutralform during recrystallization from a polar solvent, such as ethylglycolor dimethylformamide. However, it is also possible to prepare suchdyestuffs direct in this desired form if the reaction is from the startcarried out in the presence of a tertiary base, such as a tri-(C₁ -C₄-alkyl)-amine or pyridine.

When X=Cl₂ or S, or its S-C₁ -C₃ -alkyl derivative, the components areappropriately heated, without a condensing agent, in an inert solvent totemperatures of about 65°-160° C. and preferably 80°-130° C.

Examples of inert solvents which can be used are: benzene, toluene,xylene, chlorobenzene, dichlorobenzene, dichlorotoluene, chloroform,1,2-dichloroethane, perchloroethylene, dimethylformamide,dimethylacetamide, dimethylsulphoxide, sulpholane, butyrolactone, glycolmonomethyl ether, glycol monoethyl ether or pyridine.

When Y=═S.sup.⊕ -C₁ -C₃ -alkyl, anion.sup.⊖, acid acceptors areappropriately additionally employed. Acid acceptors which can be usedare organic bases, such as pyridine, triethylamine or diethylaniline,dimethylformamide or inorganic acid-binding agents, such as potassiumcarbonate, sodium bicarbonate, magnesium oxide, calcium carbonate,sodium carbonate, sodium methylate or potassium hydroxide.

A second process is to react dyestuffs of the formula ##STR14## whereinR, A, X, a and b have the abovementioned meaning and Hal represents achlorine or iodine atom or, preferably, a bromine atom, with mercaptocompounds of the formula

    Q-SH                                                       (VIII)

wherein

Q has the abovementioned meaning, and an inorganic or organic base andoptionally to cyclise the reaction products.

Organic solvents which are preferably used are polar and aprotic orprotic but free from groups which have an acid reaction in water. Thereaction is carried out in the temperature range of 50°-185° C.,preferably 85°-120° C. Bases which can be used are the customaryhydroxides, carbonates, alcoholates or acetates of alkali metals or ofammonia, such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, ammonium hydroxide, sodium methylate orpotassium acetate, or organic bases, especially tertiary organic bases,such as pyridine or triethylamine, and also anion exchange resins. Thecomponents and the base are employed in an approximately equivalentratio.

The cyclisation to give these compounds of the formula I in which Qrepresents an o-arylene radical linked to the adjacent peri-position ofring b, is carried out according to methods which are in themselvesknown (such as are described, for example, in German Offenlegungsschrift(German Published Pat. No.) 2,223,937), by diazotisation and a Sandmeyerreaction with Cu-II salts.

The starting compounds for the processes of preparation mentioned areeither known or can be prepared according to known processes. Compoundsof the formula VIII are described in German Offenlegungsschrift (GermanPublished Pat.) No. 2,233,937.

Compounds of the formula VI in which X denotes ═C(W)-are described, forexample, in German Auslegeschriften (German Published Pat. Nos.)1,201,354, 1,207,937 and 2,005,933, in German Offenlegungsschriften(German Published Pat. Nos.) 1,931,789, 2,065,552 and 2,232,449 and alsoin Journal Org. Chem. 35, (1970) 3,114-3,119 and in Chem. Abstracts(1967) 64 126 m, compounds of the formula V are described in GermanOffenlegungsschriften (German Published Pat.) Nos. 2,223,937, 2,428,198and 2,429,760 and compounds of the formula VII are described in GermanOffenlegungsschriften (German Published Pat.) Nos. 2,357,442 and1,931,789 and also in French Pat. No. 1,388,599.

The halogenation can be carried out before or after the condensationreaction with VI. Most of the mercapto compounds of the formula QSH aregenerally known compounds. Optionally substituted thiophenols aredescribed, for example, in German Offenlegungsschrift (German PublishedPat.) No. 2,116,978 or can be prepared easily from aromaticsulphochlorides under the conditions indicated in that specification.

The dyestuffs of the formula I which contain cationic groups are verysuitable for dyeing and printing acid-modified substrates, such aspolyacrylonitrile, acid-modified polyester fibres or acid-modifiedpolyamides and also for dyeing paper.

Dyestuffs of the formula I which contain acid groups are particularlysuitable for dyeing and printing polyamides and wool.

The preferred dyestuffs of the formula I, which are free from ionicgroups, are, for example, valuable disperse dyestuffs, with which it ispossible advantageously to dye and print hydrophobic fibre or fabricmaterials. Because of their good heat stability, these dyestuffs aresuitable for bulk dyeing polymeric organic materials, such aspolystyrene. The dyestuffs of the formula I possess particularlyvaluable properties on or in polyester materials, especially those madeof polyethylene glycol terephthalates. Brilliant dyeings or prints inthe orange, red, violet and blue range are obtained and most of theseare distinguished by a good affinity and good fastness properties, inparticular very good fastness to light. Comparable dyestuffs which havebeen proposed hitherto do not possess these advantages to the samedegree.

Sublimable dyestuffs of the formula I, that is to say those which arefree from ionic substituents and substituents which render the dyeingsfast to sublimation, such as sulphamoyl radicals, are also suitable fordry thermal dyeing and printing processes, especially for so-calledtransfer printing.

EXAMPLE 1

61 g of 1-ethyl-6-phenylmercapto-benz[c.d]indolin-2-one, the preparationof which is described in German Offenlegungsschrift (German PublishedPat. No.) 2,233,937, and 40 g of benzthiazolyl-2-acetamide are suspendedin 280 ml of anhydrous chlorobenzene, 60 g of phosphorus oxychloride areadded dropwise at 90° C. and the mixture is stirred for 6 hours at 105°C. After cooling to room temperature, the crystalline precipitate isfiltered off, washed with toluene and dissolved in 500 ml ofdimethylformamide at 60° C., the solution is added slowly dropwise to1.5 liters of 8% strength NaHCO₃ solution and the mixture is stirred for3 hours at room temperature. The precipitate is filtered off, washedwith water, recrystallised from ethylene glycol monoethyl ether, washedwith ethanol and dried in vacuo at 60° C. 68 g of the compound of theformula ##STR15## are obtained as a dark red crystalline powder. Adyeing on polyester fibres (130° C.) displays a red colour shade withgood fastness properties.

The dyestuffs of the formula ##STR16## which are listed in the Tablewhich follows are prepared in an analogous manner:

                Colour shade Example          (polyester) No. R U.sup.1 Q     U.sup.2 Z S.sup.1 S.sup.2 S.sup.3 S.sup.4 130°      C.                              (2) CH.sub.3 H      ##STR17##      H O H CH.sub.3 H H red (3) CH.sub.2C.sub.6      H.sub.5     ##STR18##      ##STR19##     H O H Cl H Cl red (4) n-C.sub.4      H.sub.9 Cl     ##STR20##      H S H H OC.sub.2 H.sub.5 H red (5) C.sub.2 H.sub.4      CN H     ##STR21##      Br O H C(CH.sub.3).sub.3 H H red (6) n-C.sub.3      H.sub.7 H     ##STR22##      H O H SO.sub.2 C.sub.2 H.sub.5 H H red (7) C.sub.2 H.sub.4 Cl H      ##STR23##      OC.sub.2 H.sub.5 S H H OCH.sub.3 H red (8) C.sub.2 H.sub.4 COOCH.sub.3     H      ##STR24##      OCH.sub.3      ##STR25##      H H Cl H red (9) C.sub.2 H.sub.4 OC.sub.6      H.sub.4 Br     ##STR26##      H O H CH.sub.3 CH.sub.3 H red (10) C.sub.2 H.sub.4 COOC.sub.2 H.sub.5 H      ##STR27##      H S H H Cl H red (11) n-C.sub.5      H.sub.11 H     ##STR28##      H O CH.sub.3 H H H red (12) H C.sub.2      H.sub.5     ##STR29##      H O H      ##STR30##      H H red           (13) C.sub.2      H.sub.5 H     ##STR31##      H O CHCHCHCH H H red            (14) CH.sub.3      ##STR32##      ##STR33##      H S H Br H H red (15) C.sub.2 H.sub.4      CON(CH.sub.3).sub.2     ##STR34##      ##STR35##      H O H H H H red (16) C.sub.2      H.sub.5 H     ##STR36##      ##STR37##      O H      ##STR38##      H H red (17) H H      ##STR39##      H C(CH.sub.3).sub.2 H HH H red (18) C.sub.2 H.sub.4      CN Cl     ##STR40##      H O H Br H H red

EXAMPLE 19

44.7 g of 1-ethyl-2-methylmercapto-6-phenylmercapto-benz[c.d]indoliummethosulphate are suspended in 350 ml of ethylene glycol monoethylether, 9 g of pyridine and 20.4 g of6-methoxybenzthiazolyl-2-acetonitrile are added and the mixture iswarmed to 100° C. for 3 hours and cooled. The crystalline precipitate isfiltered off, washed with ethanol and dried in vacuo at 60° C. 32 g ofthe compound of the formula ##STR41## are obtained as a dark redcrystalline powder. On polyester fibres (130° C.), the dyestuff gives ared colour shade which has good fastness properties.

EXAMPLE 20

22.6 g of the compound of the formula ##STR42## which is prepared by themethod indicated in Example 21 of German Offenlegungsschrift (GermanPublished Pat. No.) 2.357,442, are suspended in 400 ml ofdimethylformamide, 7.2 g of potassium carbonate and 6.3 g of thiophenolare added, the mixture is heated to the boil under reflux for 10 minutesand discharged into 1 kg of 5% strength acetic acid and the resultingmixture is stirred for 15 minutes. The crystalline precipitate isfiltered off, washed with water, recrystallised from 560 ml of ethyleneglycol monomethyl ether, washed with ethanol and dried in vacuo at 60°C. 21 g of the compound of the formula ##STR43## are obtained as a darkred crystalline powder. On polyester fibres (130° C.), the dyestuffgives a red colour shade which has good fastness properties. Thedyestuffs of the formula IX, which are listed in the Table which followsare obtained in an analogous manner:

    __________________________________________________________________________                                                              Colour                                                                        shade                                                                         (poly-                                                                        ester)              Ex.                                                                              R      U.sup.1  Q       U.sup.2                                                                             Z      S.sup.1                                                                         S.sup.2                                                                              S.sup.3                                                                              S.sup.4                                                                         130°         __________________________________________________________________________                                                              C.                  (21)                                                                             CH.sub.3                                                                             H                                                                                       ##STR44##                                                                            H     O      H OC.sub.2 H.sub.5                                                                     H      H red                 (22)                                                                             C.sub.2 H.sub.4 OH                                                                   H                                                                                       ##STR45##                                                                            H     O      H SO.sub.2 N(CH.sub.3).sub.2                                                           H      H red                 (23)                                                                             C.sub.2 H.sub.4 OCH.sub.3                                                            H                                                                                       ##STR46##                                                                            H     O      H                                                                                ##STR47##                                                                           H      H red                 (24)                                                                             C.sub.2 H.sub.4 Cl                                                                    ##STR48##                                                                              ##STR49##                                                                            H     S      H Br     H      H red                 (25)                                                                             n-C.sub. 3 H.sub.7                                                                    ##STR50##                                                                              ##STR51##                                                                            H     C(CH.sub.3).sub.2                                                                    H H      H      H red                 (26)                                                                             CH.sub.2CH.sub.2CH.sub.2                                                                       ##STR52##                                                                             ##STR53##                                                                          O      H OCH.sub.3                                                                            H      H red                 (27)                                                                             CH.sub.3                                                                             H                                                                                       ##STR54##                                                                            H                                                                                    ##STR55##                                                                           H CH.sub.3                                                                             SO.sub.2 N(C.sub.2                                                            H.sub.5).sub.2                                                                       H red                 (28)                                                                             C.sub.2 H.sub.5                                                                      H                                                                                       ##STR56##                                                                            H                                                                                    ##STR57##                                                                           H H      H      H red                 __________________________________________________________________________

EXAMPLE 29

14 g of 5-chloro-benzoxazolyl-acetamide are added to 19 g ofN-ethyl-4-amino-benz[k,l]thioxanthenyl-3-carboxylic acid lactam in 140ml of anhydrous chlorobenzene and 8 g of phosphorus oxychloride areadded at 80° C. and the mixture is stirred for 5 hours at 100° C. Aftercooling to room temperature, the crystalline precipitate is filteredoff, washed with toluene, recrystallised from 200 ml ofN-methylpyrrolidone, washed with dimethylformamide and then with ethanoland dried in vacuo at 80° C. 8 g of the compound of the formula##STR58## are obtained as a luminous blue crystalline powder. Onpolyester (pad-thermosol process, fixing for 30 seconds at 210° C.), areddish-tinged blue colour shade which has good fastness properties isobtained.

The dyestuffs of the formula (X) ##STR59## which are listed in the Tablewhich follows are obtained in an analogous manner:

    __________________________________________________________________________     Example                               Colour shade                           No.    R       R' R"  R'"                                                                              Z    S.sup.1                                                                            S.sup.2                                                                           on polyester                           __________________________________________________________________________    (30)  CH.sub.3 H  OCH.sub.3                                                                         H  S    H    H   reddish-tinged blue                    (31) C.sub.2 H.sub.4 CN                                                                      H  OC.sub.2 H.sub.5                                                                  H  S    H    OC.sub.2 H.sub.5                                                                  reddish-tinged blue                    (32) C.sub.2 H.sub.4 Cl                                                                      Cl Cl  H  O    CH.sub.3                                                                           H   reddish-tinged blue                    (33) C.sub.2 H.sub.4 COOCH.sub.3                                                             H  Br  H  O    H    H   reddish-tinged blue                    (34) n-C.sub.4 H.sub.9                                                                       H  CH.sub.3                                                                          H  NH   Cl   H   reddish-tinged blue                    (35) CH.sub.2 -C.sub.6 H.sub.5                                                               H  H   Cl C(CH.sub.3).sub.2                                                                  H    H   reddish-tinged blue                    (36) n-C.sub.3 H.sub.7                                                                       H  H   Br O    C.sub.2 H.sub.5 SO.sub.2                                                           H   reddish-tinged blue                    (37) H         C.sub.2 H.sub.5                                                                  H   H  S    H    H   reddish-tinged blue                    (38) --CH.sub.2 -CH.sub.2 -CH.sub.2 --                                                          H   H  O    CH.sub.3                                                                           CH.sub. 3                                                                         reddish-tinged blue                    __________________________________________________________________________

EXAMPLE 29

38 g of the compound of the formula ##STR60## the preparation of whichis indicated in Example 7 of French Patent No. 1,388,599, are suspendedin 1,000 ml of dimethylformamide, 15 g of potassium carbonate and 12.1 gof thiophenol are added, the mixture is heated to the boil for 30minutes and cooled and 10 g of glacial acetic acid are added. Thecrystalline precipitate is filtered off, washed, first with ethanol andthen with water, and dried in vacuo at 70° C. 36 g of the compound ofthe formula ##STR61## are obtained as an orange-coloured crystallinepowder. On polyester fibres, the dyestuff gives a brilliant orangecolour shade which has good fastness properties. The dyestuffs of theformula ##STR62## which are listed in the Table which follows areprepared in an analogous manner:

    __________________________________________________________________________    Example                                         Colour shade (polyester)      No.   U.sup.1     Q              A'             130° C.                __________________________________________________________________________    (40)  H                                                                                          ##STR63##                                                                                    ##STR64##     brilliant                                                                     yellowish-tinged orange       (41)  H                                                                                          ##STR65##                                                                                    ##STR66##     brilliant                                                                     yellowish-tinged orange       (42)                                                                                 ##STR67##                                                                                 ##STR68##                                                                                    ##STR69##     brilliant red-orange          (43)  Br                                                                                         ##STR70##                                                                                    ##STR71##     brilliant orange              (44)  C.sub.2 H.sub.5                                                                            ##STR72##                                                                                    ##STR73##     brilliant orange              (45)  H                                                                                          ##STR74##                                                                                    ##STR75##     brilliant                                                                     yellowish-tinged orange       (46)  H                                                                                          ##STR76##                                                                                    ##STR77##     red-orange                    (47)  Cl                                                                                         ##STR78##                                                                                    ##STR79##     reddish-tinged orange         (48)                                                                                 ##STR80##                                                                                 ##STR81##                                                                                    ##STR82##     brilliant red-orange          (49)                                                                                 ##STR83##                                                                                 ##STR84##                                                                                    ##STR85##     brilliant red-orange          (50)  H                                                                                          ##STR86##                                                                                    ##STR87##     brilliant                                                                     yellowish-tinged orange       (51)  H                                                                                          ##STR88##                                                                                    ##STR89##     brilliant                                                                     yellowish-tinged orange       (52)  Cl                                                                                         ##STR90##                                                                                    ##STR91##     brilliant orange              (53)  H                                                                                          ##STR92##                                                                                    ##STR93##     reddish-tinged orange         (54)  H                                                                                          ##STR94##                                                                                    ##STR95##     red-orange                    (55)  H                                                                                          ##STR96##                                                                                    ##STR97##     brilliant                                                                     yellowish-tinged orange       (56)  H                                                                                          ##STR98##                                                                                    ##STR99##     brilliant                                                                     yellowish-tinged orange       (57)  H                                                                                          ##STR100##                                                                                   ##STR101##    brilliant orange              (58)  H                                                                                          ##STR102##                                                                                   ##STR103##    brilliant red-orange          (59)  H                                                                                          ##STR104##                                                                                   ##STR105##    yellow-orange                 (60)  H                                                                                          ##STR106##                                                                                   ##STR107##    yellow-orange                 (61)  H                                                                                          ##STR108##                                                                                   ##STR109##    yellow-orange                 (62)  H                                                                                          ##STR110##                                                                                   ##STR111##    orange                        (63)  Cl                                                                                         ##STR112##                                                                                   ##STR113##    yellow-orange                 (64)  H                                                                                          ##STR114##                                                                                   ##STR115##    brilliant                     __________________________________________________________________________                                                    orange                    

EXAMPLE 65

41 g of the compound of the formula ##STR116## the preparation of whichis indicated in Example 7 of French Pat. No. 1,388,599, are suspended in850 ml of N-methylpyrrolid-2-one, 15 g of potassium carbonate and 12.1 gof thiophenol are added, the mixture is heated to 180° C., whilststirring, for 25 minutes, whilst distilling off water-containingsolvent, cooled and discharged into 2.5 kg of 5% strength acetic acidand the resulting mixture is stirred for 30 minutes. The crystallineprecipitate is filtered off, washed with water, recrystallised fromdimethylformamide, washed with ethanol and dried in vacuo at 70° C. 27 gof the compound of the formula ##STR117## are obtained as anorange-coloured crystalline powder. On polyester fabric (130° C.), abrilliant orange shade which has good fastness properties is obtained.

If an equivalent amount of the homologous 6-ethoxybenzthiazolyl compoundis employed in place of compound (65a), the compound of the formula##STR118## is obtained in an analogous manner. On polyester, this alsodisplays a very clear orange shade, which has good fastness properties.

Compounds with similarly valuable properties are obtained when anequivalent amount of 4-methylthiophenol, 4-chlorothiophenol,2-aminothiophenol or 5-methoxy-2-aminothiophenol is employed in place ofthiophenol.

The compound of the formula ##STR119## is also reacted by the samemethod with two equivalents of 4-methyl-thiophenol and potassiumcarbonate in N-methylpyrrolidone to give the compound of the formula##STR120## The substance is a red crystalline powder which, in a dyeingon polyester fibres, gives a brilliant scarlet shade which has goodfastness properties. The compounds of the formula ##STR121## which arelisted in the Table which follows are prepared in an analogous manner:

    __________________________________________________________________________    Ex.                                                Colour shade                                                                  (polyester)                No.                                                                              U.sup.1    U.sup.2     Q         A'             130° C.             __________________________________________________________________________    (68)                                                                              ##STR122##                                                                              H                                                                                          ##STR123##                                                                              ##STR124##    brilliant red-orange       (69)                                                                              ##STR125##                                                                              H                                                                                          ##STR126##                                                                              ##STR127##    brilliant red-orange       (70)                                                                             Br         H                                                                                          ##STR128##                                                                              ##STR129##    brilliant orange           (71)                                                                             H                                                                                         ##STR130##                                                                                ##STR131##                                                                              ##STR132##    brilliant                                                                     reddish-tinged orange      (72)                                                                             H                                                                                         ##STR133##                                                                                ##STR134##                                                                              ##STR135##    brilliant                                                                     reddish-tinged orange      (73)                                                                             H                                                                                         ##STR136##                                                                                ##STR137##                                                                              ##STR138##    brilliant                                                                     reddish-tinged orange      (74)                                                                             H          Br                                                                                         ##STR139##                                                                              ##STR140##    brilliant orange           (75)                                                                             Cl         Cl                                                                                         ##STR141##                                                                              ##STR142##    brilliant orange           (76)                                                                             H          H                                                                                          ##STR143##                                                                              ##STR144##    brilliant scarlet          (77)                                                                             H          H                                                                                          ##STR145##                                                                              ##STR146##    brilliant red-orange       (78)                                                                             H                                                                                         ##STR147##                                                                                ##STR148##                                                                              ##STR149##    red-orange                 __________________________________________________________________________

EXAMPLE 79

27.5 g of 4-amino-benz[k,l]thioxanthenyl-3-carboxylic acid lactam, thepreparation of which is described in Example 68 of GermanOffenlegungsschrift (German Published Pat. No.) 2,233,937, and 15 g of2-amino-benzthiazole are suspended in 200 ml of anhydrous chlorobenzene,17 g of POCl₃ are added dropwise at 100° C. and the mixture is stirredfor 3 hours at 105° C. After cooling to room temperature, thecrystalline precipitate is filtered off, washed with toluene,recrystallised from dimethylformamide, washed with ethanol and dried invacuo at 70° C. 3.3 g of the compound of the formula ##STR150## areobtained as a dark red crystalline powder. On polyester fibres (130° C.,under the autogeneous pressure), the dyestuff displays a brilliant redcolour shade which has good fastness properties.

Dyestuffs which have similarly valuable properties are obtained when anequivalent amount of 6-methoxy-2-aminobenzthiazole,6-ethoxy-2-aminobenzthiazole, 2-aminopyridine or 2,6-diaminopyridine isemployed in place of 2-aminobenzthiazole.

EXAMPLE 80/81

21.3 g of the compound of the formula ##STR151## which is accessible bythe method indicated in Example (65), are dissolved in 150 g of hotglacial acetic acid, 25 ml of water and 15 g of concentratedhydrochloric acid are added and a diazotisation reaction is carried outat 0° C. with a solution of 4 g of sodium nitrite in 20 ml of water. Thediazonium salt solution is allowed to run into a boiling solution of 50g of crystalline copper-II sulphate in 500 ml of 10% strength aceticacid. The mixture is boiled for a further 1 hour under reflux and thecrystalline precipitate is filtered off hot, washed with water, digestedwith 400 ml of boiling 10% strength Trilon-B solution, in order toremove copper ions, filtered off again, washed with water and dried invacuo at 70° C. 19 g of the compound of the formula ##STR152## areobtained as a dark red crystalline powder. On polyester fibres (130°C.), the dyestuff displays a bluish-tinged red colour shade which hasgood fastness properties.

EXAMPLE 82

The procedure is in accordance with the instructions of Example 1 but anequivalent amount of benzthiazolyl-2-acetic acid ethyl ester is employedin place of benzthiazolyl-2-acetamide. In this way 54 g of the compoundof the formula ##STR153## are obtained as a dark red crystalline powder.A dyeing on polyester fibres (130° C.) displays a red colour shade whichhas good fastness properties. The dyestuffs of the formula IXa##STR154## which are listed in the Table which follows are prepared inan analogous manner:

    __________________________________________________________________________                                                           Colour shade           Ex.                                                    (polyester,            No.                                                                              R    U.sup.1     Q           W          Z  S.sup.2                                                                            S.sup.3                                                                           130°            __________________________________________________________________________                                                           C.)                    (83)                                                                             CH.sub.3                                                                           H                                                                                          ##STR155## COOCH.sub.3                                                                              O  CH.sub.3                                                                           H   red                    (84)                                                                             H    H                                                                                          ##STR156## COOC.sub.2 H.sub.5                                                                       S  H    OCH.sub.3                                                                         red                    (85)                                                                             C.sub.2 H.sub.4 CN                                                                 H                                                                                          ##STR157##                                                                                ##STR158##                                                                              O  Cl   H   red                    (86)                                                                             C.sub.2 H.sub.4 Cl                                                                 H                                                                                          ##STR159##                                                                                ##STR160##                                                                              O  CH.sub.3                                                                           H   red                    (87)                                                                             n-C.sub.4 H.sub.9                                                                  Cl                                                                                         ##STR161## COOC.sub.2 H.sub.5                                                                       NH Cl   H   red                    (88)                                                                             H    H                                                                                          ##STR162## COO-n-C.sub.4 H.sub.9                                                                    S  H    H   red                    (89)                                                                             H    H                                                                                          ##STR163## CN         O  C(CH.sub.3)                                                                        H   red                    (90)                                                                             CH.sub.3                                                                            ##STR164##                                                                                ##STR165## COOC.sub.2 H.sub.5                                                                       O  OCH.sub.3                                                                          H   red                    (91)                                                                             CH.sub.3                                                                           Br                                                                                         ##STR166## CON(CH.sub.3).sub.2                                                                      O  CH.sub.3                                                                           H   red                    (92)                                                                             C.sub.2 H.sub.5                                                                     ##STR167##                                                                                ##STR168## CON(n-C.sub.4 H.sub.9).sub.2                                                             O  H    H   red                    (93)                                                                             H    C.sub.2 H.sub.5                                                                            ##STR169## CONHCH.sub.3                                                                             O  CH.sub.3                                                                           CH.sub.3                                                                          red                    (94)                                                                             H    H                                                                                          ##STR170## CN         S       OC.sub.2 H.sub.5                                                                  red                    (95)                                                                             H    H                                                                                          ##STR171##                                                                                ##STR172##                                                                              O  H    H   red                    (96)                                                                             C.sub.2 H.sub.5                                                                    H                                                                                          ##STR173##                                                                                ##STR174##                                                                              O  CH.sub.3                                                                           H   red-violet             (97)                                                                             C.sub.2 H.sub.5                                                                    H                                                                                          ##STR175##                                                                                ##STR176##                                                                              S  H    H   red-violet             (98)                                                                             C.sub.2 H.sub.5                                                                    H                                                                                          ##STR177##                                                                                ##STR178##                                                                              O  CH.sub.3                                                                           H   red-violet             (99)                                                                             H    H                                                                                          ##STR179##                                                                                ##STR180##                                                                              NH H    H   red                    __________________________________________________________________________

EXAMPLE 100

The procedure is in accordance with the instructions of Example 20 butan equivalent amount of the compound of the formula (100a) ##STR181## isemployed in place of compound (20a).

In this way 24 g of the compound of the formula ##STR182## are obtainedas a dark red powder.

Compounds (101) and (102) are also prepared in an analogous manner.##STR183##

EXAMPLE 103

The procedure is in accordance with the instructions of Example 29 butan equivalent amount of benzthiazolyl-2-acetic acid ethyl ester isemployed in place of 5-chloro-benzoxazolyl-2-acetamide. In this way 9.5g of the compound of the formula ##STR184## are obtained as a bluecrystalline powder. On polyester (30 seconds, 210° C.), a reddish-tingedblue colour shade, which has good fastness properties, is obtained.

Dyestuffs which have similar coloristic properties are obtained when anequivalent amount of 5-chloro-benzoxazolyl-2-acetic acid methyl ester,5-methyl-benzoxazolyl-2-acetic acid methylamide, benzoxazolyl-2-aceticacid piperidide, 6-methoxy-benzthiazolyl-2-acetic acid ethyl ester orbenzimidazolyl-2-acetic acid ethyl ester is employed, in each case, inplace of benzthiazolyl-2-acetic acid ethyl ester.

I claim:
 1. Dyestuff of the formula ##STR185## wherein E representshydrogen, methyl, ethyl, β-cyanoethyl, β-chloroethyl, β-acetoxyethyl,β-methoxyethyl, β-ethoxyethyl, β-hydroxyethyl, β-carbomethoxyethyl,β-carboethoxyethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl,β-phenylethyl or phenyl or conjointly with E¹ represents --CH₂ --CH₂--CH₂ --;M represents a phenyl radical which is optionally substitutedby 1-5 chlorine atoms substituted by 1 or 2 bromine atoms, substitutedby 1 or 2 C₁ -C₂ -alkyl groups, or monosubstituted by phenyl, methoxy,ethoxy, phenoxy, carboxylic acid C₁ -C₂ -alkyl ester, amino,acetylamino, or naphthyl, or conjointly with E² represents o-phenylenewhich is optionally monosubstituted by methyl, chlorine, bromine,methoxy or ethoxy; X¹ represents ═N-; B represents the remaining membersof 5-nitro-thiazole-(2)-, 3-phenyl-1,2,4-thiadiazole-(5), or5-nitro-1,3,4-thiadiazole-(2)-; E¹ represents hydrogen, ethyl, chlorine,bromine, phenylmercapto, tolylmercapto, or chlorophenylmercapto; and E²represents hydrogen, chlorine, bromine, methoxy, ethoxy, phenylmercapto,tolylmercapto, or chlorophenylmercapto.